3.

2 Diazonium Salts:
SYBSC SEMESTER-4
ORGANIC CHEMISTRY
PAPER-2

Dr. Krishnakant T. Waghmode

Associate professor
Department of Chemistry
2 Syllabus
 Preparation and their reactions/synthetic application -
Sandmeyer reaction, Gattermann reaction, Gomberg
reaction, Replacement of diazo group by -H,-OH.
 Azo coupling with phenols, naphthols and aromatic
amines, reduction of diazonium salt to aryl
 hydrazine and hydroazobenzene

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Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode
3 Diazonium salts
Diazonium compounds or diazonium salts are a
group of functional group R−N + 2X − where R can be
any organic compounds sharing a common group,
such as an alkyl or an aryl, and X is an inorganic or
organic monovalent anion, such as a halogen, -OH
etc.

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

4
1. Compounds having general formula
Ar-N=N-X are known as diazo compounds
E.g. Benzene diazonium hydroxide,
C6-H5-N=N-OH
2. Compounds with general formula
Ar-N=N-X are called diazonium salts.
e.g. Benzene diazonium chlorideC6-H5-N=N-Cl

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

5 The reaction of aniline with NaNO2 and
hydrochloric acid gives unstable salt called
benzene diazonium chloride.

Diazo group is stable only at 0-5 degree temperature

Reaction was discovered by Peter Griess in 1858.

The process of formation of Diazonium salt is called diazotization
Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021
6 Properties of Diazonium Salts

• They find application in the dye and pigment industries and

are used to produce dyed fabrics.
• Due to their property of breaking down near the ultraviolet
light, they are used in document reproduction
• They are useful in the synthesis of a large variety of organic
compounds, especially aryl derivatives.

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

7 Properties of Diazonium Salts
• Direct halogenation is not a suitable method for preparing aryl iodides
and fluorides. Nucleophilic substitution of chlorine in chlorobenzene by
a cyano group is not possible. However, diazonium salts can easily be
used to produce cyanobenzene.
• It is not possible to prepare substituted aromatic compounds by direct
substitution in benzene. For these compounds, we use the replacement
of the diazo group in diazonium salts.
• They are used as intermediates for introducing –F, –Br, –Cl, –I, –NO2, –
OH and –CN groups into the aromatic ring.

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

 8 Preparation of diazonium salt

C6H5-NH2 + Conc.HCl + HNO2

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode

05-02-2021
9 Structure of diazonium salts

 Stability is due to resonance

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

10 Mechanism of diazotization

NaNO2 + Conc. HCl 0-5 0c NaCl+ HNO2( nitrous acid)

Nitrosonium ion

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

11

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

12 Reactions of Aromatic diazonium salts

1. The reactions in which diazonium group is

replaced by monovalent substituent.
2. Both the nitrogen atoms of diazonium salt are
retained and coupled with another group

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

13 Reactions of Aromatic diazonium salts
1. The reactions in which diazonium group is replaced by monovalent
substituent.

1.Replacement of diazonium
group by halogens:

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

 14 i. Sandmeyer reaction

 Sandmeyer reaction is a type of substitution reaction that is

widely used for the preparation of aryl halides from aryl
diazonium salts. Copper salts like chloride, bromide, or iodide
ions are used as catalysts in this reaction.
 or
The Sandmeyer reaction is a chemical reaction used to
synthesize aryl halides from aryl diazonium salts using copper
salts as reagents or catalysts

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

15
Sandmeyer reaction

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16

It is an example of a radical-nucleophilic aromatic

substitution. The Sandmeyer reaction provides a
method through which one can perform unique
transformations on benzene, such
as halogenation, cyanation, trifluoromethylation,
and hydroxylation.

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

17 Reaction conditions and mechanism

 The nitrous acid is typically prepared in situ from sodium nitrite and
acid.
 Following two protonation steps, one equivalent of water is lost to form
the nitrosonium ion.
 The nitrosonium ion then acts as an electrophile in a reaction with
an aromatic (or heterocyclic) amine, such as aniline, to form a
diazonium salt, proceeding through a nitrosamine intermediate

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

18

Chlorination: ArN2+Cl–, CuCl, HCl (36% aq.), 50 – 100 °C;

bromination: ArN2+HSO4–, CuBr, HBr (48% aq.), 50 –
100 °C;
cyanation: ArN2+Cl–, CuCN, KCN, H2O,
benzene, 0 °C; hydroxylation: Cu2O, Cu(NO3)2, H2O, 25 °C.

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

19 Mechanism of Sandmeyer reaction

- -
CuCl + Cl CuCl 2
+
C6H5N2+ C6H5 + N2

- Fast
C6H5N2+
+ Cl Cu C6H5Cl + CuCl
Cl

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

20 Or Alternate

 Formation of the nitrosonium ion

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

 Formation of the benzenediazonium ion
21

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

 Single electron transfer
22

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

23 Gattermann Reaction

 In 1890 Gattermann, German scientist modified Sandmeyer reactions

 Diazonium salt is warmed with copper powder and corresponding haloacid

 Diazo group is replaced by halogen

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

24 example

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

25

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

26
Iodo group

+ -
N2 Cl
 I

+ KI
+ KCl + N 2

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

27 Replacement by fluoro group
+ - Scheimann Reaction
N2 Cl + -
 N2 BF4

+ HBF4
+ HCl
Fluoroboric acid

+ -
N2 BF4 F

+ BF3 + N2

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

 2.Replacement of diazonium group by
28 Hydroxyl group

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

29 Method is useful for preparation of Phenol

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

30 Replacement of diazonium group by -
H

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31

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32

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33

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

34 4.Replacement of Diazonium group by
cyano group

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

35

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

36 5.Gomberg reaction

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37

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

38 Preparation of Aryl hydrazines

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

39

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Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode
40 7.Azocoupling reaction

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

41

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42

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021

 Mechanism of Azocoupling
43

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44

Diazonium salts, S.Y.BSc. Organic Chemistry by Dr.K.T.Waghmode 05-02-2021